The present invention relates to 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione produced by a novel process as set forth herein and as set forth and claimed in application for United States Letters Patent Ser. No. 887,628 filed Mar. 17, 1978, now U.S. Pat. No. 4,157,350 filed on even date herewith, and novel compositions using such 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione to augment, alter, modify or enhance the flavor and/or aroma of consumable materials, or impart flavor and/or aroma to consumable materials.
There has been considerable work performed relating to substances which can be used to impart (modify, augment or enhance) flavors and fragrances to (or in) various consumable materials. These substances are used to diminish the use of natural materials, sme of which may be in short supply, and to provide more uniform properties in the finished product. Sweet, honey-like, fruity, grape-like, rose-like, ionone-like, hay-like and floral aromas with sea-amber or ambergris-like undertones and sweet-floral topnotes are desirable in several types of perfume compositions, perfumed articles and colognes.
Sweet, fruity, berry-like, fresh squeezed fruit (apple and grape) juice-like, hay-like and tea-like aromas prior to smoking and sweet, hay/tea aroma characteristics in the mainstream on smoking and sweet, tobacco-like and "fresh cigarette pack" aromas in the sidestream on smoking are particularly desirable in tobaccos and in tobacco flavoring compositions.
Compounds similar to 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione having the structure: ##STR3## have been reported in the literature, but their uses for their organoleptic properties have not been reported nor are such uses implied. Thus, the diketones having the structures: ##STR4## or their corresponding enolates having the generic structure: ##STR5## wherein a double bond could be situated at the .DELTA..sup.1 or .DELTA..sup.2 positions in the ring, or at the methylene group exocyclic to the ring, are reported by Schulte-Elte, Muller and Ohloff at Helv. Chim. Acta, Vol. 56, FASC 1 (1973) page 310 [Title: "Synthetische Ubergange von der Jonon- in die Damasconreihe"]. These compounds are, however, indicated to be useful as intermediates in synthesizing compounds of the "Damascone" series having the generic structure: ##STR6## wherein one of the dashed lines is a pi double bond and each of the other dashed lines represents single bonds, and, individually, the structures: ##STR7## which are, in turn, useful for their organoleptic properties. However, the organoleptic properties of the members of the "Damascone" series are different in kind from the organoleptic properties of 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione.
Schulte-Elte, United Kingdom Patent specification No. 1,391,736 discloses and claims a genus of compounds which includes 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione and uses of the genus members, in general, for the organoleptic properties of the members of the genus, in general; but Schulte-Elte, United Kingdom Patent specification No. 1,391,736 does not specifically teach any specific cyclohexadiene compounds per se or their uses for their organoleptic propertues. Thus, United Kingdom Patent specification No. 1,391,736 states:
"The compounds to which the invention relates have the formula: ##STR8## wherein: X represents the group: ##STR9## R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be the same or different, and each represents a hydrogen atom or a lower alkyl group having from 1 to 6 carbon atoms; and the ring is saturated or contains one endocyclic double bond in position 1, 2, 3 or 4, or an exocyclic double bond in position 2, or two conjugated double bonds in positions 1 and 3 . . . PA1 The new compounds of formula (I) include the following specific examples: PA1 2,6,6-trimethyl-1-(1,3-dioxo-but-1-yl)-cyclohex-1-ene; PA1 2-methylene-6,6-dimethyl-1-(1,3-dioxo-but-1-yl)-cyclohexane; PA1 2,6,6-trimethyl-1-(3-hydroxy-butan-1-oyl)-cyclohex-1-ene; PA1 2,6,6-trimethyl-1-(3-hydroxy-butan-1-oyl)-cyclohex-2-ene; PA1 2,6,6-trimethyl-1-(2-methyl-1,3-dioxo-but-1-yl)-cyclohex-1-ene; PA1 2,6,6-trimethyl-1-(2-methyl-1,3-dioxo-but-1-yl)-cyclohex-2-ene; PA1 2-methylene-6,6-dimethyl-1-(2-methyl-1,3-dioxo-but-1-yl)-cyclohexane; PA1 2,6,6-trimethyl-1-(2-methyl-3-hydroxy-butan-1-oyl)-cyclohex-2-ene; PA1 2-methylene-6,6-dimethyl-1-(2-methyl-3-hydroxy-butan-1-oyl)-cyclohexane; PA1 2,6,6-trimethyl-1-(2-methyl-1,3-dihydroxy-but-1-yl)-cyclohex-2-ene; PA1 2,6,6-trimethyl-1-(2-methyl-1,3-dihydroxy-but-1-yl)-cyclohex-1-ene; PA1 2,6,6-trimethyl-1-(1,3-dioxo-but-1-yl)-cyclohexane; PA1 2,6,6-trimethyl-1-(1,3-dihydroxy-but-1-yl)-cyclohexane; PA1 2,6,6-trimethyl-1-(1,3-dihydroxy-but-1-yl)-cyclohex-2-ene; and PA1 2,6,6-trimethyl-1-(1,3-dihydroxy-but-1-yl)-cyclohex-1-ene."
None of the exemplified compounds of United Kingdom Patent specification No. 1,391,736 has a chemical structure which can be considered by one having ordinary skill in the art to be even remotely similar to 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione.
In addition, the diketone having the structure: ##STR10## is indicated to be useful as a chemical intermediate at Helv. Chim. Acta 31, 2135-42 (1948) [V. Prelog and Frick, "Uber einige Oxo-tetrahydro-jonone"].
The diketone 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione of the instant invention has properties different in kind from the diketones of the prior art.